U.S. patent application number 10/476828 was filed with the patent office on 2004-11-25 for cyclodextrin particle.
Invention is credited to Schleifenbaum, Birgit, Siegel, Sven.
Application Number | 20040234479 10/476828 |
Document ID | / |
Family ID | 31724288 |
Filed Date | 2004-11-25 |
United States Patent
Application |
20040234479 |
Kind Code |
A1 |
Schleifenbaum, Birgit ; et
al. |
November 25, 2004 |
Cyclodextrin particle
Abstract
The present invention concerns flavor and/or fragrance
containing cyclodextrin particles containing cellulose ether with a
particle size in the range of from 50 to 1000 .mu.m, products
containing these particles, a process for producing as well use in
consumables, pharmaceutical products and everyday articles.
Inventors: |
Schleifenbaum, Birgit;
(Crans pres Celigny, CH) ; Siegel, Sven;
(Holzminden, DE) |
Correspondence
Address: |
Pendorff & Cutliff
5111 Memorial Highway
Tampa
FL
33634-7356
US
|
Family ID: |
31724288 |
Appl. No.: |
10/476828 |
Filed: |
November 3, 2003 |
PCT Filed: |
September 2, 2003 |
PCT NO: |
PCT/EP03/09713 |
Current U.S.
Class: |
424/70.13 ;
512/1 |
Current CPC
Class: |
A23P 10/30 20160801;
A23L 27/75 20160801; A61K 8/738 20130101; A23L 27/72 20160801; A23V
2002/00 20130101; A21D 13/45 20170101; A61K 8/731 20130101; A23L
23/10 20160801; C08J 3/122 20130101; A61K 8/0241 20130101; A23G
4/20 20130101; A61Q 11/00 20130101; A61K 2800/412 20130101; A61K
2800/56 20130101; C08L 5/16 20130101; C08J 2305/16 20130101; A21D
2/00 20130101; A23V 2002/00 20130101; C08L 5/16 20130101; A23V
2250/5108 20130101; C08L 2666/26 20130101; C08L 1/26 20130101; A23V
2250/5114 20130101; A23V 2200/224 20130101 |
Class at
Publication: |
424/070.13 ;
512/001 |
International
Class: |
A61K 007/46; A61K
007/06; A61K 007/11 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 4, 2002 |
DE |
102 40 698.7 |
Claims
1-14. (Cancelled)
15. A flavor or fragrance containing a cyclodextrin particle
comprising said cyclodextrin particle and a flavor or fragrance,
wherein said cyclodextrin particle has a particle size in a range
of 50 to 1000 .mu.m, wherein said cyclodextrin particle comprises
cellulose ether, wherein said cyclodextrin particle is obtained by
a single stage fluidized bed process from a spray mixture, and
wherein a gas introduction temperature is from 80 to 180.degree. C.
and a gas outlet temperature is from 40 to 95.degree. C.
16. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein said cellulose ether is selected
from the group consisting of methylcellulose, ethylcellulose,
ethylhydroxyethyl-cellulose, propylcellulose,
hydroxyethylcellulose, hydroxypropylcellulose,
hydroxypropylmethylcellulose, carboxymethylhydroxyethylcellulose,
carboxy-methylcellulose enthalten, and mixtures thereof.
17. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein said cellulose ether further
comprises carboxymethylcellulose.
18. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein said cyclodextrin particle has a
particle size in the range from 100 to 300 .mu.m.
19. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein said fluidized bed process is a
fluidized bed spray granulation process.
20. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein said cyclodextrin particle is
selected from the group consisting of alpha cyclodextrin, beta
cyclodextrin, gamma cyclodextrin, and mixtures thereof.
21. The flavor or fragrance containing said cyclodextrin particle
according to claim 20, wherein said cyclodextrin particle is beta
cyclodextrin.
22. The flavor or fragrance containing said cyclodextrin particle
according to claim 15, wherein an amount of said flavor or said
fragrance in said cyclodextrin particle is from 0.01 to 30 wt.
%.
23. A product comprising a flavor or fragrance containing said
cyclodextrin particle according to claim 15, wherein said product
comprises consumables, pharmaceutical products, and everyday
articles.
24. A process for producing the cyclodextrin particle according to
claim 15, said method comprising: spraying an aqueous spray mixture
in a single stage fluidized bed device, wherein said aqueous spray
mixture comprises at least one cyclodextrin, at least one flavor or
fragrance, and at least one cellulose ether.
25. The process according to claim 24, wherein a fluidized bed
device is a fluidized bed spray granulation apparatus.
26. The process according to claim 24, wherein said aqueous spray
is sprayed continuously.
27. The process according to claim 24, wherein the aqueous spray
mixture comprises 40 to 95 wt. % water, 5 to 50 wt. % cyclodextrin,
0.0005 to 15 wt. % flavor or fragrance substance, and 0.1 to 6 wt.
% cellulose ether.
28. The process according to claim 27, wherein the aqueous spray
mixture contains 60 to 80 wt. % water, 15 to 30 wt. % cyclodextrin,
0.25 to 5 wt. % flavor or fragrance substance, and 0.2 to 2 wt. %
cellulose ether.
29. A flavor or fragrance comprising a cyclodextrin particle,
wherein said cyclodextrin particle has a particle size in a range
from 50 to 1000 .mu.m, and wherein said cylodextrin particle
comprises carboxymethylcellulose.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention concerns flavor and/or fragrance
containing cyclodextrin particles containing cellulose ether with a
particle size in the range of 50 to 1000 .mu.m, products containing
these particles, a process for their manufacture as well as their
use in consumables, pharmaceutical products and everyday
articles.
[0003] 2. Description of the Related Art
[0004] Cyclodextrins are oligomers of anhydroglucose units, which
are linked via alpha-1,4 linkages into a ring shaped molecule.
Depending upon the number of the units one refers to these as alpha
(6 unit), beta (7 unit) and gamma (8 unit) cyclodextrin. These are
conventionally produced from starch by enzymatic processes. The
torroidal structure of the cyclodextrin makes possible the
formation of an enclosing complex on a molecular level. Depending
upon the geometry and polarity of the flavor material it is
possible to form more-or-less stable complexes with the guest
molecule resting stably in the polar cyclodextrin cavity.
[0005] Flavor substances are generally unstable compounds, which
exhibit high rates of loss during storage or during processing for
example in the foodstuff industry, due to evaporation or oxidation.
The cyclodextrin complexes can protect these flavor substances
against these losses.
[0006] In the case of flavor materials and fragrance materials, or
as the case may be, flavors and fragrance mixtures, these are
generally volatile, generally liquid substances, or as the case may
be, complex mixtures of these substances. It is conventional to
encapsulate these substances or substance mixtures by spray drying;
however, generally only relatively fine and irregularly structured
particles are obtained.
[0007] For the production of complexes of flavor and/or fragrance
substances enclosed with cyclodextrin, various methods are
known.
[0008] These methods include the mixing of cyclodextrin solutions,
suspensions or pastes (generally in water) and the flavor and/or
aroma substances. Depending upon the polarity of the flavor and/or
fragrance substance, there results thereby usually a two-phase
mixture. For accelerating this process one thus employs elevated
shear forces, for example involving stirring or kneading.
Subsequently there is generally a drying step, for example spray
drying, freeze drying or fluidized bed drying.
[0009] According to the known state of the art, the product of
drying by spray drying aqueous aroma/cyclodextrin complexes without
additives is very fine particles.
[0010] EP-A 392 608 describes a method for producing powdered
cyclodextrin complexes, of which the particle size is less than 12,
preferably less than 5 .mu.m. Therein processes such as, for
example, spray drying and freeze-drying are employed.
[0011] This small particle size is disadvantageous for practical
use. Fine particle cyclodextrin complexes can only be dispersed in
water with difficulty; the solubilization speed is thereby reduced.
Besides this, in the case of employment of small (typically <10
.mu.m) cyclodextrin particles in dry mixtures, which primarily
include main components with a particle size of between 50 and 500
.mu.m, there is a danger of de-mixing.
[0012] In addition, in the case of small particle sizes, it is
disadvantageous that often the pourability or flowability is
reduced and dust easily develops.
[0013] For this reason it is of advantage when the cyclodextrin
complex particles have particle sizes of at least 50 .mu.m.
[0014] During spray drying, a portion of the flavor and/or
fragrance substances remain on the surface of the particles. This
so-called surface oil leads to a reduction in the oxidation
stability and further reduces the pourability. It is preferred to
have the proportion of surface oil as low as possible.
[0015] DE-A 31 05 666 describes a process wherein particles with a
particle size of 500 to 1000 .mu.m are produced by adding a binder
to cyclodextrin complex mixtures in a kneader with subsequent
drying and grinding.
[0016] Disadvantageous with such kneading process is the high
proportion of surface oil in the finished granules. Besides this,
with regard to the manufacturing costs, the use of multiple process
steps (kneading, drying, grinding, sifting) is disadvantageous.
[0017] In EP-A 1 064 856, particles containing carbohydrates and/or
polyhydroxy compounds with sizes in the range of 100 to 400 .mu.m
are described. The therein disclosed multi-stage process for
producing these particles includes, in addition to spray drying,
further steps. One of the steps involves the return of smaller
particles formed in the process, so that these grow into the
desired particle size range by agglomeration. These particles are
disadvantageous in their low handling stability and their surface
oil content.
BRIEF SUMMARY OF THE INVENTION
[0018] The task of the present invention is comprised therein, to
provide flavor and/or fragrance containing cyclodextrin particles
with a size of at least 50 .mu.m, which avoid the above-described
disadvantages according to the state of the art and provide a
simple as possible process for production of such particles. In
addition, a narrow particle size distribution would be
advantageous.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The subject of the present invention is thus flavor and/or
fragrance containing cyclodextrin particles with a particle size in
the range of 50 to 1000 .mu.m containing a cellulose ether
obtainable by a one step fluidized bed process from a spray
mixture, wherein the gas inlet temperature lies at 80 to
180.degree. C. and the gas exit temperature at 40 to 95.degree.
C.
[0020] A further aspect of the present invention is a process for
producing cyclodextrin particles, thereby characterized, that in a
first stage fluidized bed device an aqueous spray mixture is
introduced that contains at least one cyclodextrin, at least one
flavor and/or fragrance substance and at least one cellulose
ether.
[0021] The invention further concerns products containing the
inventive cyclodextrin particles as well as the use of the
inventive cyclodextrin particles in consumables, pharmaceutical
products and everyday articles.
[0022] For producing the particles from the spray mixture various
known processes for granulation can be employed. The useful process
according to the invention is single-stage, that is, the spray
mixture is supplied to a device and, upon leaving the device, the
manufacturing is already completed and the finished cyclodextrin
particles are available. In contrast to the multi-stage processes,
no intermediate products are produced in the single-stage
process.
[0023] The particles can be produced by continuous fluidized bed
spray granulation, for example according to EP-A 163 836, or by
discontinuous fluidized bed spray granulation, for example
according to EP-A 70 719. Further, a process such as disclosed in
WO-A 97/16078 for production of flavor granules in a conventional
discontinuous operated fluidized bed rotor granulator may be
employed.
[0024] The invention is preferably carried out continuously. A
continuous process is better suited for industrial production and
exhibits shorter dwell times. For the same material throughput, bed
content in the continuous process of the fluidized bed spray
granulation is lower than in the case of a discontinuous process.
Instead of allowing all particles to grow at the same time, in the
continuous fluidized bed spray granulation only a small amount of
particle nuclei are sprayed, and, following achievement of the
desired particle size, they are immediately discharged, for example
via an air separator. The encapsulated flavor and/or aroma
cyclodextrin particles produced in accordance with the invention
exhibit a small particle size distribution; besides this the
particles (granules) can be removed selectively at the desired
size.
[0025] In the framework of the present invention, it is preferred
that the fluidized bed has a small bed height. Preferably this is 3
to 5 cm, in particularly preferred is 5 to 20 cm.
[0026] By continuous fluidized bed spray granulation, there results
from the spray mixture free flowing, low dust, granular particles.
Therein, in the ideal case, there occurs simultaneously in a
granulation apparatus the basic processes of nucleus production,
drying, formation and selective discharge of the particles that
have reached the desired particle size.
[0027] The basic principle of continuous fluidized bed spray
granulation (Chemical Engineering Technology, 62 year (1990), page
822 through 834) has been realized in countless variations. One can
distinguish in particular the variants with external nuclei
formation, in which nuclei from external sieves, grinders or other
solids storage devices are dosed or metered into the bed, as well
as variants with internal nuclei formation.
[0028] In the framework of the present invention, processes with
internal nuclei supply are preferred. One of these is described for
example in EP-A 163 836. This granulation device further utilizes a
self-regulating mechanism for particle size regulation and thus
involves minimal dwell time.
[0029] The spray mixture can be sprayed from below, from the side,
or even from above into the fluidized bed. For separation of
entrained solids from the exhaust, countless variants are possible,
which can be distinguished by the separation process (for example
cyclone or filter) or by the location of the separation step
(within or outside of the granulation apparatus).
[0030] Finally, for the discharge of particles, air separators are
preferably employed, for example as described in EP-A 332 031. With
the air separators, it is accomplished that only the large
particles are able to leave the fluidized bed. The remaining
particles remain in the fluidized bed until they have reached the
desired particle size.
[0031] For production of the inventive particles, first an aqueous
spray mixture is produced. This spray mixture contains, besides
water, at least one cyclodextrin, at least one flavor and/or
fragrance substance as well at least one cellulose ether.
[0032] From this spray mixture, the inventive particles with the
particle size of greater than or equal to 50 .mu.m are produced in
one process step in a fluidized bed temperature.
[0033] Inventive particles have a particle size of 50 .mu.m to 1000
.mu.m. Preferred are particles with a particle size of 70 pm to 500
.mu.m, and particularly preferred are 100 to 300 .mu.m.
[0034] The characterization of the particle sizes is with respect
to the particle diameter and is taken from the particle
distribution curve. This particle distribution curve represents the
dependency of the distribution sum Q.sub.3 (x) of the particle
diameters x. The distribution sum Q.sub.3 (X) is the normalized
total amount of all particles with a diameter smaller than or equal
to x. The particle size x.sub.50.3 is that particle size at which
the distribution sum Q.sub.3 (X)=0.5. Unless otherwise indicated,
all references to particle size in the present text are with
respect to the particle size x.sub.50.3. The index 3 indicates that
the type of the measured amount is the volume (Ullmanns
Encyclopedia of Technical Chemistry, Volume 3, Process Technology
I, 4.sup.th Edition, Chemical Publications, Weinheim, 1972, pages
24-34).
[0035] The particle size determination via volume distribution can
occur by laser diffraction (for example with the Master Sizer.RTM.
MSS Longbench produced by Malvern Instruments Ltd., Malvern,
UK).
[0036] Suitable cyclodextrins include alpha, beta, gamma as well as
substituted cyclodextrins. Preferred are alpha, beta, gamma
cyclodextrin or their mixtures, and preferred among these is
beta-cyclodextrin. In a preferred embodiment, the cyclodextrin of
the spray mixture is comprised solely of beta-cyclodextrin.
[0037] The proportion of cyclodextrin in the spray mixture is
preferably 5 to 50 wt. %, preferably 10 to 40 wt. %, and
particularly preferably 15 to 30 wt. %.
[0038] The proportion of water in the spray mixture is preferably
40 to 95 wt. %, more preferably at 50 to 90 wt. %, most preferably
60 to 80 wt. %.
[0039] The proportion of flavor and/or fragrance in the spray
mixture is preferably 0.0005 to 15 wt. %, more preferably 0.5 to 10
wt. %, most preferably 0.25 to 5 wt. %.
[0040] The spray mixture contains, as granulation aid, a binder,
namely cellulose ether. The cellulose ether is preferably selected
from the group including methylcellulose, ethylcellulose,
propylcellulose, hydroxyethylcellulose, hydroxypropylcellulose,
hydroxy-propylmethylcellul- ose, carboxymethylcellulose,
carboxymethylhydroxyethylcellulose and ethylhydroxyethylcellulose;
particularly preferred is carboxymethylcellulose (CMC).
[0041] The cellulose ether content of the spray mixture is
preferably 0.1 through 6 wt. %, particularly preferably from 0.2 to
2 wt. %. The dried particles preferably contain between 0.5 and 10
wt. %, particularly preferably between 2 and 4.5 wt. % cellulose
ethers.
[0042] Preferred are cellulose ethers with a viscosity of 15 to
200,000 mPas, more preferred are those with a viscosity of 1,000 to
50,000 mPas, most preferred are those with a viscosity of 5,000 to
15,000 mPas. The viscosity characteristics are determined with a 2
wt. % solution in water at 20.degree. C.
[0043] As measuring system there is used a conical plate system
with a diameter of 40 mm and a cone angle of 4.degree.. The
temperature is 20.degree. C., the shear rate is 1 s.sup.-1. The
viscosity can be determined using, for example a rheometer CVO 120
(produced by Bohlin Instruments GmbH, Pforzheim, Germany).
[0044] Following the inventive process, the proportion of flavor
and/or fragrance in the finished cyclodextrin particles is 0.01 to
30 wt. %, preferably 1 to 15 wt. % and particularly preferably 5 to
10 wt. %.
[0045] Methods for determining the loading of the surface oil are
known from the literature. In the present case the determination of
the content of flavor and/or fragrance substances in the finished
cyclodextrin particles, for determining the loading of the surface
oil, was carried out analogously to J. Agric. Food Chem. 1998, 46,
1494-1499. The methods described there were deviated from
essentially with respect to the solvents used for extraction. In
place of n-hexane, ethylacetate was used for determining the
loading and for determining the surface oil proportion a 2:1
mixture (volumetric proportion) of n-pentane and diethylether were
employed in place of n-hexane. Loading and surface oil proportion
were indicated in wt. %.
[0046] Examples of flavor and/or fragrance substances, which can be
a component of the inventive cyclodextrin particles, can be found
for example in S. Arctander, Perfume and Flavor Chemicals, Vol. I
and II, Montclair, N.J., 1969, self publication or K. Bauer, D.
Garbe and H. Surburg, Common Fragrance and Flavor Materials,
4.sup.th Ed., Wiley-VHC, Weinheim 2001.
[0047] Individual substances include the following: Extracts of
natural raw materials such as essential oils, concretes, absolutes,
resins, resinoids, balms, tinctures such as e.g., ambergris
tincture; amyris oil; angelica seed oil; angelica root oil; aniseed
oil; valerian oil; basil oil; tree moss absolute; bay (myrcia) oil;
motherwort or mugwort oil; benzoin resin; bergamot oil; beeswax
absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf
oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil;
cardamon seed oil; cascarilla oil; cassia oil; cassia absolute;
castoreum absolue; cedar leaf oil; cedar wood oil; cistus oil;
citronella oil; lemon oil; copaiba balsam; copaivabalsam oil;
coriander oil; costus root oil; cumin oil; cypress oil; davana oil;
dill weed oil; dill seed oil; eau de brouts absolue; oak moss
absolue; elemi oil; tarragon oil; eucalyptus citriodora oil;
eucalyptus oil; fennel oil; fir needle oil; galbanum oil; galbanum
resin; geranium oil; grapefruit oil; guaiac wood oil; guaiac
balsam; guaiac balsam oil; helichrysum absolue; helichrysum oil;
ginger oil; iris root absolute; iris root oil; jasmin absolute;
calmus oil; chamomile oil bleu; chamomile oil roman; carrot seed
oil; cascarilla oil; pine needle oil; mint oil; carvi oil; labdanum
oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin
oil; lavender absolute; lavender oil; lemongrass oil; lovage oil;
lime oil distilled; lime oil pressed; Bursera penicillata (linaloe)
oil; litsea-cubeba oil; bay laurel leaf oil; macis oil; marjoram
oil; mandarin oil; massoirinde oil; mimosa absolute; ambrette seed
oil; ambrette tincture; muskatelle salbei oil; nutmeg oil; myrrh
absolue; myrrh oil; myrtle oil; carnation leaf oil; carnation
blossom oil; neroli oil; olibanum absolute; olibanum oil; opopanax
oil; orange blossom absolute; orange oil; oregano oil; palmarosa
oil; patchouli oil; perilla oil; Peru balsam oil; parsley leaf oil;
parsley seed oil; clove seed oil; peppermint oil; pepper oil;
pimento oil; pine oil; poley oil; rose absolue; rose wood oil; rose
oil; rosmary oil; sage oil; lavandin; sage oil Spanish; sandalwood
oil; celery seed oil; lavender spike oil; star anis oil; styrax
oil; tagetes oil; pine needle oil; tea-tree oil; turpentine oil;
thyme oil; tolu balm; tonka absolute; tuberose absolute; vanilla
extract; violet leaf absolute; verbena oil; vetiver oil; juniper
berry oil; wine yeast oil; wormwood oil; wintergreen oil; ylang
ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon
bark oil; as well as fractions thereof, or components isolated
therefrom;
[0048] individual fragrances from the group of carbohydrates, such
as e.g. 3-caren; .alpha.-pinene; .beta.-pinene; .alpha.-terpins;
.gamma.-terpines; p-cymene; bisabalol; camphene; caryophyllen;
cedrene; farnesene; limonene; longifolene; myrcene; ocimene;
valencene; (E,Z)-1,3,5-undecatriene;
[0049] aliphatic alcohols such as e.g. hexanol; octanol; 3-octanol;
2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol;
(E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixtures of
3,4,5,6,6-pentamethyl-3- /4-hepten-2-ol und
3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol;
3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol;
4-methyl-3-decen-5-ol; the aliphatic aldehydes and their
1,4-dioxacycloalken-2-one as well as e.g. hexanal; heptanal;
octanal; nonanal; decanal; undecanal; dodecanal; tridecanal;
2-methyloctanal; 2-Methylnonanal; (E)-2-Hexenal; (Z)-4-Heptenal;
2,6-Dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal;
2,6,10-trimethyl-5,9-undecadien- al; heptanaldiethylacetal;
1,1-dimethoxy-2,2,5-trimethyl-4-hexene;
citronellyloxyacetaldehyde;
[0050] the aliphatic ketones and their oximes such as e.g.
2-heptanone; 2-octanone; 3-octanone; 2-nonanone;
5-methyl-3-heptanone; 5-methyl-3-heptanonoxime;
2,4,4,7-tetramethyl-6-octen-3-one; the aliphatic sulfur containing
compounds such as e.g. 3-methylthiohexanol;
3-methylthiohexylacetate; 3-mercaptohexanol;
3-mercaptohexylacetate; 3-mercaptohexylbutyrate;
3-acetylthiohexylacetate; 1-menthen-8-thiol;
[0051] the aliphatic nitriles such as e.g. 2-nonenoic acid nitrile;
2-tridecene acid nitrile; 2,12-tridecadiene acid nitrile;
3,7-dimethyl-2,6-octadiene acid nitrile; 3,7-dimethyl-6-octene acid
nitrile;
[0052] the aliphatic carboxylic acids and their esters such as e.g.
(E)- and (Z)-3-hexenylformate; ethylacetoacetate; isoamylacetate;
hexylacetate; 3,5,5-trimethylhexylacetate;
3-methyl-2-butenylacetate; (E)-2-hexenylacetate; (E)- and
(Z)-3-hexenylacetate; octylacetate; 3-octylacetate;
1-octen-3-ylacetate; ethylbutyrate; butylbutyrate; isoamylbutyrate;
hexylbutyrate; (E)- and (Z)-3-hexenylisobutyrate; hexylcrotonat;
ethylisovalerianate; ethyl-2-methylpentanoate; ethylhexanoate;
allylhexanoate; ethylheptanoate; allylheptanoate; ethyloctanoate;
ethyl-(E,Z)-2,4-decadienoate; methyl-2-octinate; methyl-2-noninate;
allyl-2-isoamyloxyacetate; methyl-3,7-dimethyl-2,6-oct-
adienoate;
[0053] the acyclic terpene alcohols such as e.g., citronellol;
geraniol; nerol; linalool; lavadulol; nerolidol; farnesol;
tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol;
2,6-dimethyloctan-2-ol; 2-methyl-6-methylen-7-octen-2-ol;
2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol;
3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol
2,6-dimethyl-2,5,7-octatrien-1-ol; as well as their formates,
acetates, propionates, isobutyrates, butyrates, isovalerianates,
pentanoates, hexanoates, crotonates, tiglinates,
3-methyl-2-butenoates;
[0054] the acyclic terpene aldehydes und-ketones such as e.g.
geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal;
7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal;
geranylacetone; as well as the dimethylund diethylacetales of
geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
[0055] the cyclic terpene alcohols such as e.g. menthol;
isopulegol; alpha-terpineol; terpinenol-4; menthan-8-ol;
menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalooloxide;
nopol; cedrol; ambrinol; vetiverol; guaiol; as well as their
formiates, aceates, propionates, isobutyrate, butyrate,
isovalerianates, pentanoates, hexanoates, crotonates, tiglinate,
3-methyl-2-butenoates;
[0056] the cyclic terpenaldehydes and ketones such as e.g.
menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor;
fenchon; alpha-ionon; beta-ionon; alpha-n-methylionon;
beta-n-methylionon; alpha-isomethylionon; beta-isomethylionon;
alpha-irone; alpha-damascone; beta-damascone; beta-damascenone;
delta-damascone; gamma-damascon;
1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;
1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H-
)-one; nootkatone; dihydronootkatone; alpha-sinensal;
beta-sinensal; acetylated cedar wood oil (methylcedrylketone);
[0057] the cyclic alcohols such as e.g. 4-tert.-butylcyclohexanol;
3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol;
2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol;
2-isobutyl-4-methyltetrah- ydro-2H-pyran-4-ol;
[0058] the cycloaliphatic alcohols such as e.g.
alpha,3,3-trimethylcyclohe- xylmethanol;
2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol;
2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol;
2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol;
3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol;
3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;
3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol;
1-(2,2,6-trimethylcyclohexyl)pentan-3-ol;
1-(2,2,6-trimethylcyclohexyl)he- xan-3-ol;
[0059] the cyclic and cycloaliphatic ethers such as e.g. cineol;
cedrylmethylether; cyclododecylmethylether;
(ethoxymethoxy)cyclododecane; alpha-cedrenepoxide;
3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan;
3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan;
1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-dien; roseoxide;
2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxan-
;
[0060] the cyclic ketones such as e.g. 4-tert-butylcyclohexanone;
2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone;
2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one;
3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one;
3-methyl-2-pentyl-2-cyclo- penten-1-one;
3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone- ;
3-methylcyclopentadecanone;
4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohe- xanone;
4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one;
6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)indanone;
5-cyclohexadecen-1-one; 8-cyclohexadecen-1-one;
9-cycloheptadecen-1-one; cyclopentadecanone;
[0061] the cycloaliphatic aldehydes such as e.g.
2,4-dimethyl-3-cyclohexen- carbaldehyde;
2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexencarbaldehyde;
4-(4-methyl-3-penten-1-yl)-3-cyclohexencarbaldehyde;
[0062] the cycloaliphatic ketones such as e.g.
1-(3,3-dimethylcyclohexyl)-- 4-penten-1-one;
1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;
2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphtalenylmethylketone;
methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienylketone;
tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone;
[0063] the esters of cyclic alcohols such as e.g.
2-tert-butylcyclohexylac- etate; 4-tert butylcyclohexylacetate;
2-tert-pentylcyclohexylacetate; 4-tert-pentylcyclohexylacetate;
decahydro-2-naphthylacetate;
3-pentyltetrahydro-2H-pyran-4-ylacetate;
decahydro-2,5,5,8a-tetramethyl-2- -naphthylacetate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenylacetate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenylpropionate;
4,7-methano-3a,4,5,6,7,7a-hexahydro-5, or 6-indenylisobutyrate;
4,7-methanooctahydro-5, or 6-indenylacetate;
[0064] the esters of cycloaliphatic carboxylic acids such as e.g.
allyl-3-cyclohexylpropionate; allylcyclohexyloxyacetate;
methyldihydrojasmonate; methyljasmonate;
methyl-2-hexyl-3-oxocyclopentanc- arboxylate;
ethyl-2-ethyl-6,6-dimethyl-2-cyclohexencarboxylate;
ethyl-2,3,6,6-tetramethyl-2-cyclohexencarboxylate;
ethyl-2-methyl-1,3-dioxolan-2-acetate;
[0065] the aromatic carbohydrates such as e.g. styrene und
diphenylmethane;
[0066] the araliphatic alcohols such as e.g. benzylalcohol;
1-phenylethylalcohol; 2-phenylethylalcohol; 3-phenylpropanol;
2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol;
2,2-dimethyl-3-(3-methylphenyl)propanol;
1,1-dimethyl-2-phenylethylalcoho- l; 1,1-dimethyl-3-phenylpropanol;
1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol;
3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol;
4-methoxybenzylalcohol; 1-(4-isopropylphenyl)etha- nol;
[0067] the esters of araliphatic alcohols and aliphatic carboxylic
acids such as e.g. benzylacetate; benzylpropionate;
benzylisobutyrate; benzylisovalerianate; 2-phenylethylacetate;
2-phenylethylpropionate; 2-phenylethylisobutyrate;
2-phenylethylisovalerianate; 1-phenylethylacetate;
alpha-trichlormethylbenzylacetate;
alpha,alpha-dimethylphenylethylacetate;
alpha,alpha-dimethylphenylethylbu- tyrate; cinnamylacetate;
2-phenoxyethylisobutyrate; 4-methoxybenzylacetate; the araliphatic
ethers such as e.g. 2-phenylethylmethylether;
2-phenylethylisoamylether; 2-phenylethyl-1-ethoxyethylether;
phenylacetaldehyde dimethylacetal; phenylacetaldehydediethylacetal;
hydratropaaldehyde dimethylacetal; phenylacetaldehyde
glycerinacetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane;
4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin;
4,4a,5,9b-tetrahydro-2,4-dime- thylindeno[1,2-d]-m-dioxin;
[0068] the aromatic and araliphatic aldehyde such as e.g.
benzaldehyde; phenylacetaldehyde; 3-phenylpropanal;
hydratropaaldehyde; 4-methylbenzaldehyde;
4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-d-
imethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal;
2-methyl-3-(4-tert-butylphenyl)propanal;
3-(4-tert-butylphenyl)propanal; cinnamaldehyde;
alpha-butylcinnamaldehyde; alpha-amylcinnamaldehyde;
alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal;
4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde;
4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylendioxybenzaldehyde;
3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal;
2-methyl-3-(4-methylendioxyphenyl)propanal;
[0069] the aromatic and araliphatic ketones such as e.g.
acetophenone; 4-methylacetophenone; 4-methoxyacetophenone;
4-tert-butyl-2,6-dimethylace- tophenone; 4-phenyl-2-butanone;
4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone;
benzophenone; 1,1,2,3,3,6-hexamethyl-5-indany- lmethylketone;
6-tert-butyl-1,1-dimethyl-4-indanylmethylketone;
1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanon-
e;
5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-aceto-naphthone;
[0070] the aromatic and araliphatic carboxylic acids and their
esters such as e.g. benzoic acid; phenylacetic acid;
methylbenzoate; ethylbenzoate; hexylbenzoate; benzyl-benzoate;
methylphenylacetate; ethylphenylacetate; geranylphenylacetate;
phenylethyl-phenylacetate; methylcinnamate; ethylcinnamate;
benzylcinnamate; phenylethylcinnamate; cinnamylcinnamate;
allylphenoxyacetate; methylsalicylate; isoamylsalicylate;
hexylsalicylate; cyclohexylsalicylate; cis-3-hexenylsalicylate;
benzylsalicylate; phenylethylsalicylate;
methyl-2,4-dihydroxy-3,6-dimethy- lbenzoate;
ethyl-3-phenylglycidate; ethyl-3-methyl-3-phenylglycidate;
[0071] the nitrogen containing aromatic compounds such as e.g.
2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzol;
3,5-dinitro-2,6-dimethyl-- 4-tert-butylacetophenone; cinnamic acid
nitrile; 5-phenyl-3-methyl-2-pente- ne acid nitrile;
5-phenyl-3-methylpentane acid nitrile; methylanthranilate;
methy-N-methyl-anthranilate; Schiff's bases of methylanthranilate
with 7-hydroxy-3,7-dimethyloctanal,
2-methyl-3-(4-tert-butylphenyl)propanal or
2,4-dimethyl-3-cyclohexencarba- ldehyde; 6-isopropylchinolin;
6-isobutylchinolin; 6-sec-butylchinolin; indol; skatole;
2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazi- ne;
[0072] the phenols, phenylethers und phenylesters such as e.g.
estragole; anethole; eugenole; eugenylmethylether; isoeugenole;
isoeugenylmethylether; thymol; carvacrol; diphenylether;
beta-naphthylmethylether; beta-naphthylethylether;
beta-naphthylisobutylether; 1,4-dimethoxybenzol; eugenylacetate;
2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol;
p-cresylphenylacetate;
[0073] the heterocyclic compounds such as e.g.
2,5-dimethyl-4-hydroxy-2H-f- uran-3-one;
2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one;
3-hydroxy-2-methyl-4H-pyran-4-one;
2-ethyl-3-hydroxy-4H-pyran-4-one;
[0074] the lactones such as e.g. 1,4-octanolide;
3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide;
8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide;
1,5-decanolide; 1,5-dodecanolide; 1,15-pentadecanolide; cis- and
trans-11-pentadecen-1,15-olide; cis-und trans-12-pentadecen-1,15-
-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-olide;
10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide;
12-oxa-1,16-hexadecanolide; ethylen-1,12-dodecandioate;
ethylen-1,13-tridecandioate; coumarin; 2,3-dihydrocoumarin;
octahydrocumarin.
[0075] Examples of aromatic substances that would be suitable as
components of the cyclodextrine particles are, besides all the
above mentioned compounds, primarily the following classes of
compounds: aliphatic esters (saturated and unsaturated) e.g.
ethylbutyrate, allylcapronate; aromatic esters e.g. benzylacetate,
methylsalicylate; organic aliphatic acids (saturated and
unsaturated) e.g. butyric acid, acetic acid, caprionic acid;
organic aromatic acids; aliphatic alkohols (saturated and
unsaturated) e.e. ethanol, propylene glycol, octenol, 3-ocetenol,
cis-3-hexenol; cyclic alcohols e.g. menthol; aromatic alcohols e.g.
benzyl alcohol; aliphatic aldehydes (saturated and unsaturated)
e.g. acetaldehyde, nonadienal; aromatic aldehyde e.g. benzaldehyde;
ketone e.g. menthon; cyclic ethers e.g. 4-hydroxy-5-methylfuranone;
aromatic ether e.g. p-methoxybenzaldehyde, guaiacol; phenolic
ethers e.g. methoxyvinylphenol; acetale e.g. acetaldehyde
diethylacetal; lactones e.g. gamma-decalactone; terpenes e.g.
limonene, linalool, terpines, terpineol, citral (geranial und
neral); sulfur containing compounds e.g. dimethylsulfide,
methylthiol, ethylthiol, allylisothiocyanate, methylfuranthiol,
difurfuryldisulfide or pyrazine e.g. methylpyrazine,
acetylpyrazine.
[0076] Due to the very small proportion of surface oil on the
inventive cyclodextrin particles, these are particularly suitable
for encapsulation of very fragrance-intensive, very volatile,
easily oxidized, difficult to control and/or pour substances. There
can be mentioned in this context for example acetaldehyde,
allylisothiocyanate, limonene, cis-3-hexenol, citral,
methylethylpyrazine or methylthiol.
[0077] Besides this, the inventive cyclodextrin articles can
contain nutritional compounds or mixtures of compounds
(nutraceuticals). There can be mentioned for example panthenol,
pantothenic acid, essential fatty acids, Vitamin A und derivates,
carotine, Vitamin C (ascorbic acid), Vitamin E (tocopherol) and
derivates, vitamins of the B- and D-series such as Vitamin B.sub.6
(nicotinamide), Vitamin B.sub.12, Vitamin D.sub.1, Vitamin D.sub.3,
Vitamin F, folic acid, biotin, amino acids, compounds of the
elements magnesium, silicon, phosphorus, calcium, manganese, iron
or copper, coenzym Q10, unsaturated fatty acids, .omega.-3-fatty
acids, polyunsaturated fatty acids, .gamma.-linolic acid, oleic
acid, eicosapentaoic acid, docosahexanoic acid and their derivates,
bisabolol, chloramphenicol, caffein, capsaicin, prostaglandin,
thymol, camphor, extracts or other products of plant and animal
origin, e.g. evening primrose oil, borage oil or currant seed oil,
fish oil, cod liver oil, ceramide and ceramide like compounds.
Plant extracts such as e.g. arnika, aloe, barbers' itch, ivy,
stinging nettles, ginseng, henna, chamomile, ringlet flower,
rosemary, legend (Folia Salviae), box blade or thyme. Oils such as
apricot seed oil, avocado oil, babassu oil, cotton seed oil, borage
oil, thistle oil, peanut oil, gamma-oryzan oil, haws seed oil, hemp
oil, hazelnut oil, currant seed oil, jojoba oil, cherry seed oil,
salmon oil, flax oil, corn oil, macadamia nut oil, almond oil,
evening primrose oil, mink oil, olive oil, pecan nut oil, plum seed
oil, pistachio nut oil, rape seed oil, rice germ oil, castor oil
plant oil, safflower oil, sesame seed oil, soy oil, sunflower oil,
tea tree oil, grapes kernel oil or wheat germ oil.
[0078] It is of course possible that the inventive cyclodextrin
particles can include further substances such as for example
emulsifiers, colorants, anti-oxidants, stabilizers, UV-absorbers,
vitamins and other ingredients conventional in the consumable, body
care, pharmaceutical or flavor and fragrance industry.
[0079] The production of the spray mixture can occur for example as
described in EP-A 1 084 625 or as described below.
[0080] First, a complex of cyclodextrin and the flavor substance is
formed. For this, cyclodextrin and flavor must be brought at least
partially into solution. As solvent, one could employ water at a
temperature of 10.degree. C. to 90.degree. C., preferably from
40.degree. C. to 70.degree. C., particularly preferably 50 to
60.degree. C. For flavor substances with particularly low boiling
points or high temperature sensitivities, temperatures of 15 to
30.degree. C. are preferred.
[0081] Depending upon the polarity of the flavor and/or fragrance
substance, the result is usually a two-phase mixture. Shear forces
are preferably used to accelerate the process. The introduction of
the shear forces can occur, for example by stirring or, as the case
may be, dispersing, wherein rotor-stator dispersing apparatus or
high pressure homogenizers, among others, are suitable.
[0082] The movement or biasing of the true equilibrium in the
direction of the flavor and/or fragrance cyclodextrin complex takes
time. In accordance with the invention, the batch is stirred with
introduction of shear forces preferably 0.2 to 24 hours with
cooling to 4 to 25.degree. C., preferably 8 to 16 hours with
cooling to 4 to 7.degree. C.
[0083] In the case of sensitive or delicate flavor and/or fragrance
substances the rest time is preferably shortened to 15 to 30
minutes at 4 to 7.degree. C.
[0084] The addition of cellulose ethers into the spray mixture can
occur at any point in time. This could be prior to complex
formation, during complex formation, following complex formation
but prior to cool storage, during cool storage or after cool
storage. It is also possible to mix the cellulose ether with the
cyclodextrin powder and subsequently to introduce the mixture into
the water. The addition of the total amount of the cellulose ether
can also be subdivided into multiple fractions, which is
proportioned, and added at varying time points.
[0085] In the production of the spray mixture, the addition of the
feed stock can occur in any sequence. For example, cyclodextrin and
cellulose ether can be mixed, subsequently added to water and
intensively stirred or, as the case may be, dispersed. Subsequently
flavor and/or fragrance substances can be added and the mixture
intensively stirred or, as the case may be, dispersed and cool
stored. An alternative sequence comprises first the intensive
mixing of water, cellulose ether and flavor and/or fragrance
substance as well as the subsequent addition and the dispersion of
cyclodextrin. In a further exemplary variation, cyclodextrin can be
added to water and intensively stirred. The flavor is added to this
and dispersed. Following the subsequent cool storage, the cellulose
ether is added and distributed by stirring or, as the case may be,
dispersing.
[0086] Granulation occurs preferably at a granulation temperature
as described in EP-A 163 836. The temperature of the spray mixture
is selected in such a manner that there is no decomposing or
destabilizing of the flavor or, as the case may be, fragrance
cyclodextrin complex. The temperature is generally between 5 and
70.degree. C., preferably between 10 and 40.degree. C. and
particularly preferably between 20 and 30.degree. C.
[0087] As fluidizing gas, one could employ, for example air,
nitrogen, argon or carbon dioxide, and preferred are air and
nitrogen. The gas inlet and gas outlet temperatures of the
fluidizing gas are to be adapted to the respective spray mixtures.
The gas inlet temperature is between 80 and 180.degree. C.,
preferably between 100 and 140.degree. C., and particularly
preferably between 120 and 130.degree. C. The gas outlet
temperatures lies between 40 and 95.degree. C., preferably between
45 and 70.degree. C., particularly preferably between 50 and
60.degree. C.
[0088] The inventive cyclodextrin particles can be employed in a
variety of products. In nutritional and snack goods these could be
employed for example in sweets such as for example hard candies,
chewing gum, breath mints, comprimates, hard caramels,
confectioneries and chocolate, baked good such as cakes, waffles or
wafers and small cakes, snacks, instant meals as well as other
instant products (soups, sauces, powdered and granulated drinks,
tea bags, spice mixtures). The cyclodextrin particles are
particularly suitable for heated, high heated, warmed, sterilized
or pasteurized consumables such as, for example, catered foods,
fried foods, chips, flavored panades, precooked foods, microwave
foods as well as fruits and vegetable preserves.
[0089] Pharmaceutical products can include for example dissolvable
tablets, throat or cough lozenges, pharmaceutical powders or
granulates.
[0090] Everyday articles could be, for example, body care products,
house care products, tobacco wares, (for example cigarettes),
cosmetic products, laundry, dishwashing or detergent compositions,
air fresheners, textiles or odor absorbing substances, for example
cat litter.
[0091] Body care products can include for example oral care
products such as toothpaste, tooth gel, dental creams, dental care
gum and mouth wash.
[0092] The following examples further explain the invention:
[0093] Unless indicated otherwise, all proportions are with respect
to weight.
[0094] The term retention (indicated in wt. %) will in the present
case be understood to mean the weight-dependent relationship of the
amount of flavor and/or fragrance substance in the finished
particle in comparison to the amount of flavor and/or fragrance
substance employed in the spray mixture.
EXAMPLES
Example 1
Limonene--Cyclodextrin Particle
[0095] Ingredients:
[0096] 13,143 g drinking water
[0097] 4,000 g beta-cyclodextrin (Kleptose.RTM. beta-cyclodextrin,
produced by Roquette)
[0098] 431 g d-limonene
[0099] 133 g carboxymethylcellulose (CMC)(Walocel CRT 10000 GA
available from the company Wolff Walsrode, Germany)
[0100] viscosity of a 2% solution at 20.degree. C., 1 s.sup.-1:
1,000 mPas
[0101] The water was warmed to 25.degree. C., the cyclodextrin was
added and the formulation was mixed for 3 minutes using an Ultra
Turrax T50 DPX. The d-limonene was added, and the batch was
dispersed for an additional 15 minutes.
[0102] After the mixture was stored for 6 hours at 6.degree. C.,
the carboxymethylcellulose was added and homogenized using the
Ultra Turrax T50 DPX. Thereafter, the batch was stirred for an
additional 15 hours at 20.degree. C. and subsequently introduced
into the fluidized bed granulation apparatus.
[0103] In a granulation apparatus of the type described in EP-A 163
836 (with the following features: diameter inflow base: 225 mm,
spray nozzle: 2-material nozzle; fluidized output: zigzag air
separator; filter: internal hose filter), the above described spray
mixture was granulated. The temperature of the mixture was at
35.degree. C. For fluidizing the bed content, air in an amount of
60 kg/h was blown in. The inlet temperature of the fluidized gas
was at 120.degree. C. The temperature of the output gas was at
55.degree. C. As separating gas, air in amount of 1.5 kg/h was
supplied at a temperature of 34.degree. C. The granulation yield
was approximately 420 g/h. A free flowing granulate with an average
particle size of 131.7 .mu.m and a flow density of 470 g/l was
obtained. The granulate exhibited a flat surface and spherical,
substantially ball-shaped geometry.
[0104] On the basis of the constant pressure loss of the filter and
the likewise constant remaining bed content, this can be referred
to as a stationary condition with respect to the granulation
process.
[0105] load: 7.7%
[0106] retention: 79.2%
[0107] surface oil: 0.03%
[0108] particle size distribution (using laser diffraction; device:
Malvern Master Sizer.RTM. MSS Longbench):
[0109] Q3 (x)=0.1: x=75 .mu.m
[0110] Q3 (X)=0.5: x=132 .mu.m
[0111] Q3 (x)=0.9: x=196 .mu.m
[0112] powder density: 470 g/l
Example 2
Limonene Particle 2
[0113] 6,385 g drinking water
[0114] 2,000 g beta-cyclodextrin
[0115] 215.5 g d-limonene
[0116] 78 g carboxymethylcellulose (CMC), Tylose.RTM. C 6000 G1
produced by the company Clariant
[0117] viscosity of a 2% solution at 20.degree. C., 1 s.sup.-1
mPas: 6,000 mPas
[0118] The water was warmed to 50.degree. C., the cyclodextrin was
added, and the formulation was stirred for 3 minutes using an Ultra
Turrax T50 DPX. The d-limonene was added and the batch was
dispersed for an additional 15 minutes.
[0119] After the mixture was stored for 30 minutes at 20.degree.
C., the carboxymethylcellulose was added and homogenized with the
help of the Ultra Turrax mixer.
[0120] Thereafter, the batch was allowed to rest for an additional
15 hours at 6.degree. C. and was subsequently supplied to the
fluidized bed granulation apparatus of Example 1. The inlet
temperature of the fluidizing gas was 125.degree. C. The
temperature of the output gas was 49.degree. C. Granulation
produced approximately 570 g/h. A free flowing granulate with an
average particle size of 165.8 .mu.m and a powder density of 460
g/l was obtained. The cyclodextrin particles exhibited a flat outer
surface and a spherical, substantially ball shaped geometry.
[0121] loading: 8.4%
[0122] retention: 86.4%
[0123] surface oil: 0.04%
[0124] particle size relationship (laser diffraction):
[0125] Q3 (x)=0.1: x=89 .mu.m
[0126] Q3 (x)=0.5: x=166 .mu.m
[0127] Q3 (x)=0.9: x=272 .mu.m
[0128] powder density: 460 g/l
Example 3
Peppermint Aroma Particles
[0129] 6,385 g drinking water
[0130] 2,000 g beta-cyclodextrin
[0131] 215.5 g peppermint aroma
[0132] 62 g carboxymethylcellulose (CMC) (Walocel CRT 1000 GA of
the company Wolff Walsrode, Germany) viscosity of the 2% solution
at 20.degree. C., 1 s.sup.-1 mPas: 10,000 mPas
[0133] The water was warmed to 50.degree. C., the cyclodextrin was
added and the batch was mixed for 3 minutes with an ultra turrax
T50 DPX. After addition of the peppermint aroma, the batch was
mixed thoroughly for an additional 15 minutes with the ultra turrax
T50 DPX. CMC was added and dissolved with the ultra turrax.
[0134] The storage and further production occurred analogous to
Example 2, the granulation output was 600 g/h. A free flowing
granulate was obtained.
[0135] loading: 8.8%
[0136] retention: 87%
[0137] particle size distribution (as determined by laser
diffraction; device: Malvern Master Sizer.RTM. MSS Longbench):
[0138] Q3 (x)=0.1: x=103 .mu.m
[0139] Q3 (x)=0.5: x=182 .mu.m
[0140] Q3 (X)=0.9: x=296 .mu.m
[0141] surface oil: 0.03%
[0142] powder density: 400 g/l
Example 4
Beef Flavor Particles
[0143] 6,385 g drinking water
[0144] 2,000 g beta-cyclodextrin
[0145] 200 g beef meat flavor
[0146] 95 g methylcellulose (MC), Methocel.RTM. A4M FG, Dow
Chemical Company
[0147] viscosity of a 2% solution at 20.degree. C., 1 s.sup.-1
mPas: 4,000 mPas
[0148] After addition of the cyclodextrin in water (10.degree. C.)
the formulation was stirred for 3 minutes with an Ultra Turrax T50
DPX. The beef meat flavor was added and the batch was dispersed for
an additional 40 minutes. After the mixture has allowed to rest for
30 minutes at 20.degree. C. the methylcellulose was added and
homogenized with the Ultra Turrax mixer.
[0149] Storage and further production occurred analogously to
Example 1.
Examples 5-14
[0150] Composition of spray mixtures, the indication is with
respect to the employed amount in gram.
1 5 6 7 8 9 10 11 12 13 14 water 6200 6000 6000 6385 6385 6500 6500
6385 6800 6900 alpha-cyclodextrin 660 2000 0 0 0 0 0 0 0 0
beta-cyclodextrin 660 0 0 2000 2000 2000 2000 2000 2000 2000
gamma-cyclodextrin 660 0 2000 0 0 0 0 0 0 0 carboxymethyl- 55 55 55
0 0 0 0 0 0 0 cellulose (Walocel .RTM. CRT 10000 GA) hydroxypropyl-
0 0 0 90 0 0 0 0 0 0 methylcellulose methocel .RTM. K4MFG
ethylcellulose 0 0 0 0 60 0 0 0 0 0 propylcellulose 0 0 0 0 0 70 0
0 0 0 hydroxyethyl- 0 0 0 0 0 0 90 0 0 0 cellulose Tylose MH 4000
P2 hydroxypropyl- 0 0 0 0 0 0 0 60 0 0 cellulose ethylhydroxyethyl-
0 0 0 0 0 0 0 0 60 0 cellulose carboxymethylhydro 0 0 0 0 0 0 0 0 0
90 xyethyl-cellulose lemon oil 200 150 230 10 1 250 100 50 200
75
Example 15
Comparison
[0151] In Table 1, the advantages with respect to oxidation
stability, flowability and redispersibility of the particles
produced in accordance with the invention as compared to particles
that are produced in accordance with the state of the art become
clear. The better oxidation stability is determined by the lower
proportion of surface oil.
2TABLE 1 Cyclodextrin- Particles According per containing d- to the
EP-A 392 per limonene invention 608 DE-A 31 05 666 Embodiment
Example 2 Kneading, Kneading, drying grinding, spray sifting drying
Process Batchwise Batchwise Continuous Batchwise preparing
preparing extrusion preparation of of the of the and the mix, batch
spray mix, spray mix, granulation drying, batch continuous,
continuous grinding, simultaneous simultaneous batch sifting drying
and drying and granulation no granulation Particle size 50
.mu.m-300 .mu.m 0.05 .mu.m-5 .mu.m 500-1000 .mu.m 500-1000 .mu.m
Pourability 32.degree. 63.degree. 52.degree. 47.degree. (angle of
pouring) Redispersibility at 4 0 3 3 20.degree. C. Surface oil
0.04% 0.40% 2.4% 0.19% Retention 86% 74% 92% 86% Oxidation 0 3 5 3
sensitivity (after 180 days)
[0152] Flowability was determined in accordance with DIN ISO 4324.
A pour angle <300 means a very good flowability, a pour angle
between 30.degree. and 40.degree. means a free flowability and a
pour angle >45.degree. means a poor flowability (see also
Uhlemann, Moehrl: Fluidized Bed Spray Granulation,
Springer-Publishers Berlin, 2000, page 169).
[0153] Oxidation sensitivity was evaluated following storage times
of one day or, as the case may be, 180 days (storage temperature
20.degree. C.). Respectively 100 g samples were filled into a 250
ml plastic bottle which was tightly closed with a lid. Following
the respective storage times the bottles were opened and evaluated
as to smell. The evaluation was based on a scale of 0 (no oxidation
smell) to 5 (strong oxidation smell). After one day all particles
of Table 1 were still in basically sound condition.
[0154] Redispersibility was checked in the following way: in a
beaker glass 20 ml water (20.degree. C.) and 200 mg of the
respective particles were added and stirred for 1 minute at 200
min.sup.-1 with a magnetic stirrer. Evaluation was based on a scale
of 0 (very poor redispersibility) to 5 (complete redispersibility).
Very poor redispersibility was indicated when, following the
stirring, not all of the particles were wetted or hydrated with
water, had formed large agglomerates and/or if following a stand
time of 1 minute, many particles sank to the floor.
Example 16
Chewing Gum with Peppermint Flavor
[0155] In a chewing gum (B) 2 wt. % of peppermint
flavor-cyclodextrin product of Example 3 (corresponding to 0.18 wt.
% flavor) and 1.12 wt. % peppermint flavor in fluid form were
worked in. For comparison, a chewing gum (A) was produced, which
contained 1.30 wt. % peppermint flavor in liquid form. Sensory
time-intensity studies using a skilled test group (12 persons)
showed overall a significantly higher flavor intensity with chewing
gum (B) with peppermint flavor-particles. After 15 minutes, the
peppermint flavor-cyclodextrin product containing sample had twice
as high a flavor intensity.
[0156] X=chewing duration in minutes
[0157] Y=peppermint flavor intensity
[0158] A=chewing gum with liquid peppermint flavor
[0159] B=chewing gum with liquid peppermint flavor+peppermint
flavor-particles
[0160] The peppermint flavor intensity was evalated on a scale of
from 0 (no peppermint flavor) to 10 (very strong peppermint
flavor).
Example 17
Wafers
[0161] The limonene-cyclodextrin product of Example 2 was added in
an amount of 1.2 wt. % (corresponding to 0.1 wt. % flavor) to a
wafer batter comprised of flour, water, sugar, lecithin, salt and
peanut oil. Wafers were baked at a temperature of 200.degree. C.
for 1 minute. For comparison, liquid limonene was added in the same
concentration to the batter and mixed into the same ingredients.
The sensory evaluation of fresh product (1 day old) demonstrated a
higher flavor intensity in the wafers with the
limonene-cyclodextrin product. As shown in Table 2, sensory
evaluation could be confirmed.
3 TABLE 2 Wafers with 0.1 wt. % limonene as cyclodextrin Wafers
with 0.1% complex limonene (liquid) Limonene content 2533 ppm 755
ppm in the baked wafer Retention 95% 38% following baking
limonene-note 3 0 (following storage) Off-flavor 0 4 Sensorial
fresh, citrus flat, oxidized, description rancid
[0162] The sensory evaluation of the flavor intensity of the
limonene note and the off-flavor occurred following 4-month storage
at 20.degree. C., on a scale of from 0 (not detectable) to 5 (very
strong).
[0163] The term retention (indicated in %) is in the present case
understood to mean the weight based relationship of the amount of
limonene in the waffle in comparison to the employed amount of
limonene.
Example 18
Instant Soup
[0164] To a powder mixture comprising salt, starch, seasoning
powder, fat powder and dried vegetable were added, for reinforcing
the fresh green note, cis-3-hexenol-cyclondextrin particles, which
were produced analogously to Example 1.
[0165] As a result of the employed particle size of 100 to 200
.mu.m, the following properties were found during the mixing
process: free of dust, low danger of coming out of mixture, good
flowability.
[0166] During the storage, cis-3-hexenol in the cyclodextrin
complex was well protected against oxidization, in particular on
the basis of the low proportion of surface oil in the particles
produced in accordance with the present invention.
[0167] Following pouring of the instant soup mixture into water at
80.degree. C., the complex dissolves within a few seconds.
* * * * *